CA1206873A - Absorbing material containing an isothiazolin-3-one; use thereof as an agent for body hygiene and process for preparing the same - Google Patents

Abstract

ABSTRACT DESCRIPTION

The invention relates to the field of personal hygiene. Its purpose an absorbent material consisting of a hydrocolloid polyelectrolyte insoluble in water and absorbing several times its weight in liquid aqueous and an isothiazoline derivative - one - 3.

Preferably this absorbent material also includes a metal salt and the isothiazoline-one-3 derivative has the formula following general:

in which:

R is a hydrogen atom or a C1 to C4 alkyl group, R 'is a hydrogen atom or a C1 to C4 alkyl group or a halogen, Y is a hydrogen atom or a C1 to C4 alkyl group.

Application of these absorbent materials to the production of articles for use unique for personal hygiene.

Description

31 Z ~) ~ 873 OYE - 3, APPLICATION TO BODY HYGIENE AND DO PROC
TENTIONS OF THIS

The invention relates mainly to the field of personal hygiene.
It relates to an absorbent material consisting of a polyelectrolyte hydrocolloldal insoluble in water and absorbing several times its weight in aqueous liquid.

It also relates to an application of this material and a method obtaining it.

STATE OF THE ART

We know that urine, originally sterile [except in case of urinary defection is contaminated, as soon as it leaves the urethra, with the flora of the perineum which is the seat of a large number of bacteria, 80 of which are formed by:

Profus (50%), Klebsiella, PseudomQnas, Colt.

Urine is also an excellent growth substrate for these germs.

From mcmc the menstrual blood which contains proteins, various amines and lipids, constitutes a culture medium for the bacteria mentioned more high.

thus urea is trans ~ rmee in ammonia thanks to the ureases that have hundreds of bacteria, such as Protes and Klebsiella, around your following reeactlon:

NH2 ukase C = O That 4 NH3 (urea) ., L2 ~) 6 ~ 73 The amino acids constituting the proteins are also subjected to degradation which led to the formation of ammonlac.

Other bodies, like blood lipids, are also transformed in other degradation products according to the following scheme:

CHU - O - C - R CHU OH
CH - O - C - R CH OH + 3 RCOOII
o CHU - O - C - R CHU OH
o Triglycerides Glycéroi o f Hey O - C - R Que OH
CH OC CH OH 2 RCOOH Hey P04 + BsOH
Jo Que O - P - B CHU y of Phospholipids Glycerol R = Derivatives of fatty acids B = Lamb alcohol function The fatty acids formed are among other things ugly butyric, isobutyric and isovaleric.

All these reactions resulting from the activity of bacteria have as common characteristic of leading to very odor compounds desag rab le.

In individuals with urinary or fecal incontinence and in women in menstrual period, this flora of the perineum is directly in contact with bodily fluids absorbed by the absorbent pad, this which leads to the formation of bad odors due to the activity of bacteria on these fluids. We can see that this phenomenon, at the limit tolerable when it comes to a baby, becomes psychologically painful to bear for an adult.

,,. hilum In order to eliminate this drawback, it has been proposed to combine a bactericide to absorbent mattresses of diapers and periodic towels.

Thus the French patent Born 2490093 (LANDSTINGENS INKOPSCENTRAL
5 RELATED EKONOMISK FAINÉANT) describes the incorporation, preferably in the surface, of a water-soluble copper salt in an absorbent mattress formed from cellulose fibers. Copper, in ionic form, is indeed known for its bactericidal and fungicidal activities.

This technique has, however, certain drawbacks. The typeface rigid deposited on the mattress is aggressive towards the skin of the user: this can lead to certain dermatological accidents and even weaken natural keys.
!
15 The industrial implementation of the process also presents certain difficulties because it is necessary to treat the entire surface of the mattress absorbent.

In addition, the deposition methods (spraying, soupoudra ~ e) have 20 a significant danger for the personnel.

he European patent Born 0019371 UNI LEVER offers cl incorporate an ion of a transition metal (such as copper or zinc) in a tara improved retention additive which is, like its name 25 I'indiclue, a body inGorpQr ~ absorbent mattress to improve its sapacit ~ s absorption. I t is established an ionic bond between the groups an ionic (including COOL and the transition metal ion This bond is sufficiently labile to allow the ion of the transitional motel to mire out of lira in the buffer and cause clotting of 30 large proteins. In order to obtain the migration of these ions out of lira it is, however, necessary to incorporate a relatively large amount important since about 80 of the COOII groups are neutralized.
This has the drawback of limiting the gel setting speed of will read and decrease its absorption capacity.

~ L2 ~ 6 5173 We know from slush that transition metals like copper or zinc are bactericides, therefore toxic, and toxicologically speaking it is preferable that these are present in very low doses.

The object of the invention is to provide a super absorbent having a bactericidal activity that can be communicated to its environment constituted by the absorbent mattress. What has the advantage eliminate the risk of skin irritation before the arrival of the Liquid naked.

In common parlance the term "super absorbent" is synonymous additl ~ with improved retention or material absorbing several times its weight in liquid.

GENERAL DESCRIPTION OF THE INVENTION

The invention is characterized in that the absorbent material comprises at least minus one isothiazoline - oye - 3 derivative of general formula:
R, o y` Su Y
In which:

Y is a hydro ~ ene atom, a linear C1-C1 alkyl group or ramiti ~, a cycloalky! e group in Ci to Ci, R is a hydrogen atom, a C1-C1 alkyl group or a allogeneic, R 'is a hydrogen atom, a C1-C1 alkyl group or a allogeneic.

~ Z06 ~ 3 one concerning the application, Invention is characterized in that the absorbent material is used as an additive with improved retention, incorporated in absorbent mattresses intended for personal hygiene, especially those intended for baby or adult diapers 5 incontinents, or periodical protections.

Regarding the process for obtaining the material, Invention is characterized in that, in a water-alcohol mixture, a first at least one isothiazoline derivative - oye - 3 then the 10 hydrocolloldal polyelectrolyte, the mixture then being filtered.

- POLYECLECTROLYTES - HYDROCOLLO ~ DAUX
.
HydrocollQIda-Jx polyelectrolytes insoluble in lobs and absorbent many times their weight in aqueous liquid can be halved main categories namely natural polyelectrolytes on the one hand and synthetic polyelectrolytes on the other hand (see in particular US 4043952).

1) The natural polyelectrolytes are advantageously chosen from among the an ionic derivatives of starch or cellulose or dextran still called polysaccharides. Among the anionic groupings are may cite the carboxyl, sulfonate, sulfate or phosphate. The preferred anionic groups are the groups carboxylalkyl and in particular the carbo ~ y ~ thyle groups and Roy hile These anionic groups are preferably neutralized by a alkaline action such as sodium or by a primary, secondary amine or tertiary in a proportion greater than 40 compared to total number of Ionic troops and preferably between 40 and 85 y. This, as is well known, improves the ability absorption of polymers These polyelectrolytes are in crosslinked form so as to make them insoluble in water but obviously without altering their capacity absorption.
This articulation can result from the formation of covalent bonds by means of esterification or etherification which can be ensured -y lZ ~) 6 ~ 73 by dols, dihaloyenurest epichlorohydrins as in ES (A born I wash), The articulation can also be ensured by metals of transition belonging to the following groups of the classification periodic: lll B, IV B, VB, Vu B, Vu l B, Vu ll B, lll A, IV A, VA, Vu A. Among these, mention may be made of aluminum, zirconium, chromium, titanium, zinc.

2) Homopolymers or copolymers of carboxylic acids established like polyacrylic or methacrylic acids (see in particular US
4043952) or homopolymers or copolymers containing acids sulfonic like those from acid polymerization -) sulfonics established.
These homopolymers or copolymers are also in the form an ionic, partially or totally, and are crosslinked by the same means as described in 1).
The polymers used are those comprising the car ~ oxyl groups and especially polyacrylic or polymethacrylic acid.

All of these polymers absorb between five and several hundred times their weight in aqueous liquid depending on whether it is water, urine, without, y including menstrual blood.

!
As an indication, methods like those described in patents y DE-2702781 or F ~ -23051 ~ 52 can be used to determine the ) degree of absorption.

Another important parameter for these polymers lies in their gel setting speed. A good polymer must have a 30 as low a freeze as possible by referring for example to the Cortex t G. Goldstein and M. Pierre, Marketing Technology Service Insight 81, Section IX-1-18, Miller Freeman Publication. ).

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06f5 73 The derivatives which are described by your general formula are known per se as well as their bactericidal activity.

The patentability of the invention does not lie in this biocidal activity already known but in the faculty that these compounds reveal to be able mirror out of the hydrocolloldal polyelectrolyte and interfere, otherwise dom peach, the development of bacteria throughout the absorbent mattress and thus preventing the formation of bad odors.

The following patents describe these derivatives as well as their process of preparation:

* OR 2139421 where we will find an exhaustive list of isothia-zolien - oye - 3.
* US 3517022 where we will find the preparation and the biocidal properties isothiazollne derivatives - oye -3.
* and also US 3544480, US 37614 ~ 8, FR 2398505.

Among all the derivatives which correspond to the general formula, we will prefer derivatives having a formula in which:
Y is a hydrogen atom or a C1-C6 alkyl group R is a hydrogen atom or a C1 to C1 alkyl group R 'has the same if ~ nitication as previously And, preferably, those having a general formula in which:
Y is a methyl bearing Pu is a hydrogen atom Pu is a hydrogen atom or an allogene or a methyl group.

The halogen can be, in particular, chlorine or bromine. In a way to have improved bactericidal activity while retaining the ability migrants specific to these derivatives it is desirable that the material absorbent contains at least two derivatives, one (A corresponding to the general formula in which R 'is a range, such as chlorine, and 5; ~ 8 ~ -3 preferably corresponding to the following formula:
R. Jo Hey \ S hi R being a hydrogen atom or a C1 to Ci alkyl group Y being a hydrogen atom or a C1-C1 alkyl group!
Hai is preferably chlorine.

The other Bu corresponding to the general formula in which R 'is a hydrogen atom, a C1-C1 alkyl group and, preferably, with the following formula:

R, R 'being a hydrogen atom or a C1 to C alkyl group Y being a hydrogen atom THAT a C1 to C1 allcyl group R being a hydrogen atom or a C1 to C1 alkyl group De preferenc ~ the absorbent material comprises the two derivatives following:
H Jo H t>

ce S / y os \ Clt3 AB
Known under the following official names:

A - chlorinated - 5 - methyl - 2 - isothiazoline - oye - 3 B - mestizo - 5 - methyl - 2 - isothiazoline - oye - 3 hi The mixture of these products is sold by the American Society OHM HUAS under the CAHOTONS brand. CG (R) which contains 1.5%
about isothiazoline-oye-3 derivatives (1.2% of A and 0.3 of Bu and 98.5% inert material by weight.

This preference, for absorbent materials which contain the derivatives FA) and (B), the molar ratio between these two compounds is understood between 0-, 5 and 8.

Although it is possible to incorporate the isothiazoline - oye - 3 derivative in a wide range of proportion by weight with respect to polyelec-trolyte without departing from the invention, it is preferable that the material a-outgoing comprises a proportion by weight of isothiazollne derivative -oye - 3 relative to the polyelectrolyte between 1.5 and 750 ppm and preferably between 7.5 and 450 ppm and even better from 10.5 to 150 ppm.

As it was written above and this is what makes the interest of lnvention, isothiazoline derivatives - oye - 3 put outside the polyelectrolyte. It was found that it was entirely possible and even desirable that the material also contains a metal ion of a salt of transition metal known for its bactericidal activities and coagulants are preferably copper or zinc.

These ions can be present in the form of halide or salts or ~ aniqlles. We will find a description of it with a number exhaustive in Fi 24900 ~ 3.

However, halides are preferred.

surprisingly, this reduces the amount of derivative isothia ovine oye - 3 required, which is very interesting in terms of toxicological, and, moreover, while the isothiazoline derivative - oye -

3 miter, metal Ilion remains in the polymer which ensures further improved bactericidal coverage. In addition, the setting speed gel is increased.

Preferably, the weight ratio of isothiazoline derivative - oye - 31 salt of a transition metal is between ~, 012 and 0, ~ 18.

These absorbent materials according to the invention, when they are disseminated in the form of grains or powder in absorbent pads in known proportions to allow sufficient absorption, eliminate odors whose origin has been discussed in the preamble.

The absorbent material according to the invention is obtained at a friendly temperature yawning preferably with an eaulmethanol or fall blend in proportions between 80/20 and 90/10.

When the absorbent material contains a metallic Delon salt it is pro-maple to incorporate this before the isothiazoline derivative - oye - 3.

The absorbent material is introduced into the mattress, known manner, in several different ways, of which we can locate:

- Continuous or discontinuous deposition between two layers of bluff (cellulose fiber A particularly interesting asbestos from this process is illustrated by the European patent Born 22792.

- Mixing with the bluff.
This bluff is then sandwiched between cotton wool sheets or nonwoven.

EXAMPLES

All the tests were carried out with the compound isothiazoline - oye - 3, resulting from the mixture of the following two derivatives:

A - chlorinated - 5 mestizos - 2 isothiazoline - oye - 3 B - methyl - 5 methyl - 2 isothiazoline - oye - 3 (CAHOTONS CG of the Rhum Huas Company.

-,.

vtj ~ 73 GENERAL PROCEDURE Obtaining COMPARED ABSORBENT MATERIAL
BOTH THE CG CAHOTONS AND IONIC COPPER
. _. . ..

In a methanol / water mixture t8D / 20), the metal ion SOU is added form of cupric chloride then the CAHOTONS CG and finally the fold electrolyte.

The proportions are as follows in parts by weight:

- polyelectrolyte 100 - COHOTONS CG 1,5 - Cru Key 3 After filtration, the polymer powder associated with the two is recovered other compounds. Methanol is recycled.

.
SPEED read FREEZE

The following three polyelec ~ rolytes have been tested:

With known polycarboxyl starch known as the SA ~ WET trade mark from the SANYO Company.
B Polyacrylate deigns alkali metal known under the brand of corNnerce l ~ QU ~ XEEP from SEITE: Errr ~ SU ~
C Carboxymethyl starch known under the trademark AKUCELL from AKZO.

Gold Using the so-called CORTEX test (see description of polyelectro-lyres} the following results are obtained for the gel setting speed (in s):

BLOOD URINE

100 cc 100 cc 2 g B 3 "26"

with Cahotons CG
+ Or ++ 2.5 "y

4 of C 19 "120"

with brass CG
+ Or ++ 16.5 "57"

It is therefore quite surprising that the presence of the bactericidal compounds significantly improves the speed of treatment.
KIL.

MIGRATION OF BACTERI ~ :: IDES

Inhibition zone method -.

Paper discs, on which some quantity of product to be tested, are placed on seeded agar with a specific micro-organism axis: Pseudomrnes Elevés hi The Petri dishes are placed in the refrigerator for 24 h., Then in the oven for 18 h. at 30 C.

After incubation, the total diameter of the zones of inhibition is measured.
appeared:

DIAMETER TEST PRODUCTS IN THE QUANTITY OF COTTON AREA
DEPOSITED QUANTITIES OF CORRESPONDING INHIBITION
BY DISC
B 3.3 mg 18 mm 0 B + Or ++ 3.3 mg 18 mm 0

5% Or What 5 mg 29 mm 0.37 g B 10 mg 34 mm 0.63 g COHOTONS CG 15 mg 39 mm 0.9 ~ g 20 mg 42 mm 1.24 g B + 5 mg 28 mm O, 33 9 10 mg 34 mm û, 63 g K, '\ T ~ ION CG
Or y + 15 mg 38 mm 0.88 g y Cousis 20 mg 40 mm 1.05 g EU EMPLOYED
MUSE OF INTENSITY FE ODOR

We kit sllbir to a sample of people the three kinds of tests follow:

- determination of the detection threshold concentration C. S) of a odorant tStei ~ er Chef. Teak. Vol 1 April 1971), - Establishment of the standard curve with various samples containing multiples of the threshold concentration.

- determination of the activity of the bactericide by evaluation of the ion site of the odor, this being almost Fiée in unit C. S.

y 517 ~
you The test according to the example is carried out on a kind of towel periodicals containing lira A with 0.1 or 0.15 of CAHOTONS CG and 0 2% of Or Key Relative to the weight of the towel. A try comparison was also made.

7 ml of beef blood are deposited per towel and 1 ml of suspension bacterial prepared by mixing:
1 ml of a 24-hour culture of Pseudomonas aeruginosa 1 ml """" of Escherichia Colt 10 0 ml """48 h of Klebsiella Pneumonia 5 ml """" of Protes Mirabilis - Each towel is then placed in the polyethylene bottle, `then incubated for 15 h at 30 ~ C. The measurement of The intensity of the odor is done under the same conditions.

The results are as follows:

Bump CG 0.10% 4 Bump CG 0 15%
Control (without bactericides) 6 t Changes renf ~ rmane de lira B tAquakeeP) modified (5 of Ou 2 and 2 brass) removed doors for 12 hours by incontinent mat A control batch without modified AXA has goose tests in parallel.
almost 12 hours, an olfactory measurement and a measurement of urine pH
changes have been made.

~ 06 ~ 3 Results:
AXA untreated AXA treated Number of exchanges tested 43 56 Number of smelly changes 14 0 average pH 8, 5 7, 3 The presence of bactericides on lira therefore decreases significantly lasting, appearance of smelly products, and limits the increase in pH of urine, thereby reducing its irritant power.

Claims (14)

The realizations of the invention, about which a right exclusive ownership or lien is claimed are defined as follows: - 1. Absorbent material consisting of a hydrocolloid polyelectrolyte insoluble in water and absorbing several times its weight in liquid aqueous, characterized in that it comprises at least one iso- derivative thiazoline-one-3 of general formula:

in which Y is a hydrogen atom, a linear C1 to C8 alkyl group or branched, a C3 to C6 cycloalkyl group.

R is a hydrogen atom, a C1-C4 alkyl group or a halogen.
R 'is a hydrogen atom, a C1 to C4 alkyl group or a halogen 2. absorbent material according to claim 1, characterized in that Y is a hydrogen atom or a C1 to C4 alkyl group.

R is a hydrogen atom or a C1 to C4 alkyl group.

R 'has the same meaning as in claim 1. 3. Absorbent material according to claim 2, characterized in that Y is a methyl group R is a hydrogen atom R 'is a hydrogen atom or a group methyl or halogen. 4. Absorbent material according to claim 1, characterized in that it comprises at least two isothiazoline-one-3 derivatives, A - at least one corresponding to the formula in which R 'is a halogen.
B - at least one other responding to the formula in which R 'is a hydrogen atom or a group C1 to C4 alkyl. 5. Absorbent material according to claim 4, characterized in that it comprises the two derivatives isothiazoline-one-3:

6. Absorbent material according to one of the claims tions 4 or 5, characterized in that the proportion in mole A / B is between 0.5 and 8. 7. Absorbent material according to claim 1, characterized in that it comprises the isothia derivative zoline-one-3 in a proportion by weight included between 1.5 and 750 ppm compared to the polyelectrolyte. 8. Absorbent material according to claim 7, characterized in that it comprises the isothia derivative zoline-one-3 in a proportion by weight included between 7.5 and 450 ppm compared to the polyelectrolyte. 9. Absorbent material according to claim 1, characterized in that the isothiazoline-one-3 derivative is associated with a salt of a transition metal. 10. Absorbent material according to claim 9, characterized in that the transition metal is chosen from copper and zinc. 11. Absorbent material according to one of the claims tions 9 or 10, characterized in that the ratio in isothiazoline-one-3 derivative weight / metal salt transition is between 0.012 and 0.018. 12. Method for obtaining an absorbent material according to claim 1, characterized in that in a water-alcohol mixture in proportions included between 80/20 and 90/10, we add at first at least one isothiazoline-one-3 derivative then the poly-hydrocolloid electrolyte and in that we filter then. 13. Method for obtaining an absorbent material according to claim 12, characterized in that add a salt of a transition metal before the poly-hydrocolloid electrolyte. 14. Absorbent pad for personal hygiene, especially those intended for baby diapers or for incotinous adults, or with periodic towels, characterized in that it comprises an absorbent material according to one of claims 1, 2 or 3.